5-nitrothiazoleazo-nu, nu-substituted aniline-compounds



Patented July 13, 1954 UNITED STATES TENT OFFICE 5-NlTROTHIAZOLEAZO-N,N-SUB$TITUTED ANI L IN E Q COMPOUNDS J oseph B." Dickey-and Edmund B. Towne, Kingsport,-Tenn., assignors to Eastman Kodak Company, Rochester, Y., a corporation of: New

Jersey No Drawing. Application December 21, 1951, Serial No. 262,903

9 Claims.

Where R represents a'member selected fromthe group consisting of an alkyl group havingl to 10, inclusive, carbonatomsyanalkoxyalkyl group having 3 too, inclusive, carbon atoms; a hydroxyalkyl group having- 2 to 5,-inclusive, carbon atoms, a cyanoalkyl'group having 2m 6, in'-' elusive, carbon atoms, a sulfoalkyl group: having 2 to inclusive, carbon atoms, a sulfatoalkyl group having 2 to 5;- inclusive,- carbon atoms, aphosphatoalkyl' group having? to 5, inclusive; carbon atoms, a phosphonoalkyl group having, 2 to" 5, inclusive, carbon atoms, a fl-nitroethyl group; i an alkenyl groupi having .2 1304,: inclusive, carbon atoms and: a (CH2)m-COO'Rz-group, wherein m' isselected iroinil, 2 and 3iaml R2 represents an al-kyl group. having 1 tol, irrclusive, carbon atoms, Ri represents a member selected from the group ccnsisting or a phenyl group, a xenyl group and a pyridyl group, X represents a member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6, inclusive, carbon atoms, a cyano group, a trifiuoromethyl group and a group, wherein Qirepresents a member'selected from the group. consistingof a hydrogen atom; anitro' group, a c-hlorine'atom, a bromine atom and analkyl group, havin'g lto 4, inclusive; car bon'atoms, Z represents amember selected-from the group consisting of'an alkyl' group having l to 4, inclusive, carbon atoms, an alkoxy group having 1 to l, inclusive,- carbon atoms, a chlorine atom, a bromineatom, a fluorine-atom and a group, wherein Y represents an alkyl group hav-- ing 1 to 3, inclusive, carbonatoms and n is-se lected from 0, 1 and 2, are valuable dyes for color-- ing textile materials made of or containing a cellulose alkyl car-boxylio-acid ester havingtwo to four carbon atoms in theacid groups thereof.- They are especially 0f-usefor the coloration 0f cellulose acetate textile materials.- When applied to the-aforesaid textile materials tl-iey-give-- violet, reddish-blue, blue and-greenish-bluedye= ings which have good -fastness to-light-and gas The compounds ofour invention also color wool; silk, nylon, polyethylene terephthalate and modified polyacrylonitrile textile materials similar colors but donotappeartobe as good dyes for these latter materials as they are for-cellulose acetate.

It is an. object or our-invention to-providenetvazo compounds. Another object is to-providea satisfactory. process -for the preparation of I our-- new azo compounds, A further object is to-prm videdyed textile -materials, especially: cellulose" acetate textile materials, which have good fastmess to light anal gas;

By cellulose alkyl carboxylic acid esters having, two to four carbon. atoms in theacid groupsthereof, we mean to include for example, bothhydrolyzedandunhydrolyzeol cellulose acetate, cellulose propionate, cellulose butyrate,-celluloseacetate-propionate and cellulose acetate-butyrate.

The new azo compoundsof our invention are? prepared-by diazot-izing 1 a Z-am-ino-Bmitrothiazole having the formula:

R; R1, X; z anu in' the fore oing-formulashave: the meaningipreviously' 'assigned to them;

Typical of I the 2 -ami-n'O 5 nitrothiazolcom pounds used in the preparation of the azo compounds of our invention are: 2-amino-5-nitrothiazole, 2-amino-4-methyl-5-nitrothiazo1e, 2- amino 4 ethyl 5 nitrothiazole, 2 amino 4-n-butyl-5-nitrothiazole, 2-amino-4-n-hexyl-5- nitrothiazole, Z-amino-4-cyano-5-nitrothiazole, 2 amino 4 trifluoromethyl 5 nitrothiazole, 2-amino-4-phenyl-5-nitrothiazo1e, 2-amino-4- (o-nitrophenyl) -5-nitrothiazo1e, 2-amino-4- (m nitrophenyl) -5nitrothiazole, 2-amino-4-(p-nitrophenyl) -5-nitrothiazole, 2-amino-4- (p-chlorophenyl) -5-nitrothiazole, 2-amino-4- (o-bromophenyl) -5-nitrothiazole, 2-amino-4- (o-fluorophenyl) -5-nitrothiazole, 2-amino-4-(o-chlorophenyl)-5-nitrothiazole, 2-amino-4-(p-fluorophenyl) -5-nitrothiazole, 2-amino-4- (o-methylphenyl) -5-nitrothiazole, 2amino-4- (p-methylphenyl -5-nitrothiazole and 2-amino-4-(p-n butylphenyl)-5-nitrothiazole. The use of 2- amino-5-nitrothiazole is ordinarily preferred.

Illustrative of the alkyl groups represented by R are the methyl, the ethyl, the n-propyl, the isopropyl, the n-butyl, the n-amyl, the n-hexyl, the n-heptyl, the n-octyl, the n-nonyl and the n-deoyl groups. Illustrative of the alkoxyalkyl groups represented by R are the fi-methoxyethyl, (B-ethoxyethyl, B-n-propoxyethyl, B-n-butoxyethyl, the n-propoxypropyl, the 2,3-dimethoxypropyl, the 3-methoxy-2-hydroxypropyl and the 3-methoxy-2-methy1-2-hydroxypropyl groups. Similarly, the 6-hydroxyethyl, the B-hydroxypropyl, the y-hydroxypropyl, the [3,Y-dihYdI'OXY- propyl, the ,e-methyl-fin-dihydroxypropyl, the B-hydroxybutyl, the e-hydroxyamyl and the 5,6- dihydroxyamyl groups are illustrative of the hydroxyalkyl groups R represents. Illustrative of the cyanoalkyl groups R represents are the [3- cyanoethyl, the -cyanopropyl, the t-cyanobutyl and the e-cyanopentyl groups.

Sulfoalkyl groups represented by R include, for example, the p-sulfoethyl, the y-sulfopropyl and the a-sulfobutyl groups. Sulfatoalkyl groups represented by R include, for example, the fi-sulfatoethyl, the e-sulfato-n-propyl, the 7-5111- fatropropyl, sulfated firy-dihydroxypropyl, the a-sulfatobutyl and the e-sulfatoamyl groups. Illustrative phosphatoalkyl groups represented by R are the e-phosphatoethyl group, the -phosphatopropyl group, the 6-phosphatobuty1 group and the e-phosphatoamyl groups. Phosphonoalkyl groups represented by R include, for example, the ,B-phosphonoethyl, the 'y-phosphonopropyl, the fi-phosphonobutyl and the e-phosphonoamyl groups. The vinyl, the allyl, the methallyl and the crotyl groups are illustrative of the alkenyl groups R represents. Illustrative of the (-CH2)m-COOR2 groups R represents are the -CH2COOCH3, the -CH2CO0C2H5, the -CH2COOCH2CH2CH2CH3, the

--CH2CH2COOCH3 -CH2CH2COOC2I-I5 the -CH2CH2COOCHzCIlzCl-IzCI-I3, the

-CH2CH2CH2COOCH3 the --CH2CH2CH2COOC2H5 and the -CH2CH2CH2COOCH2CH2CH2CH3 groups.

Similarly the methyl, the ethyl, the n-propyl, the isopropyl, the n-butyl, the secondary butyl and the tertiary butyl groups are illustrative of the alkyl groups represented by Z and Q. Illustrative of alkoxy groups represented by Z are the methoxy, the ethoxy, the n-propoxy, the isopropoxy and the n-butoxy groups. The methyl, the ethyl, the n-propyl and the isopropyl groups are illustrative of the alkyl groups represented by Y.

The following examples illustrate the azo compounds of our invention and their manner of preparation:

EXAMPLE 1 A. Preparation of nitrosyl sulfuric acid 1.52 grams of sodium nitrite were added portionwise to 10 cc. of concentrated sulfuric acid, with stirring, and the temperature of the reaction mixture was allowed to rise to 65 C. The resulting solution was then cooled to 5 C. and 20 cc. of a mixture of 3 cc. of propionic acid and 17 cc. of acetic acid were added dropwise, with stirring, while allowing the temperature to rise to 15 C. and maintaining it at this temperature during the remainder of the addition.

e to 6 parts by volume of acetic acid).

B. Diazotzzation The nitrosyl sulfuric acid mixture prepared as described above was cooled to 0 C.-5 C. and then 2.9 grams (0.02 mole) of 2-amino-5-nitrothiazole were added portionwise, while stirring, after which 20 cc. of a propionic-acetic acid mixture prepared as described above were added while keeping the temperature of the reaction mixture at 0 C.-5 C. The reaction mixture thus obtained was then stirred at about 0 C.-5 C. for three hours and excess sodium nitrite present in the mixture was destroyed by adding one to two grams of urea. A clear diazonium solution was obtained.

C. Coupling 12 cc. of the 2-amino-5-nitrothiazole diazonium solution prepared as described in 13 above were added, with stirring, at 0 C.-5 C. to a solution of 1.14 grams of N-fi-hydroxyethyl-N-phenyl-mtoluidine in 10 cc. of a 1:6 mixture of propionicacetic acid (i. e. 1 part by volume of propionic acid After a short time the reaction mixture was made neutral to Congo paper by adding sodium acetate portionwise and the coupling reaction was allowed to proceed for three hours. The reaction mixture was then poured into cold water (15 C.) and after stirring a short time, it was filtered to recover the dye compound formed on the filter. The dye compound thus obtained was washed well with water and dried. 1.44 grams of the dye compound having the formula:

were obtained. This compound has excellent affinity and color value for cellulose acetate textile materials and colors them deep, bright reddish-blue shades having good fastness to light and excellent fastness to gas. The dyeings also have excellent discharge properties. The dye compound also colors nylon, wool and silk textile materials deep reddish-blue shades.

EXAMPLE 2 12 cc. of the 2-amino-5-nitrothiazole diazonium solution prepared as described in B of Example 1 were added, with stirring, at 3 C. to a solution of 1.29 grams of N-p -dihydroxypropyl-N- phenyl-m-toluidine in 10 cc. of a 1:6 mixture of propionic acid-acetic acid. Upon working up the reaction mixture in accordance with the procedure described in Example 1, 1.61 grams of dye were obtained as a dark powder. It colors cellulose acetate textile materials reddish-blue shades having good fastness to light, excellent fastness to gas and excellent discharge properties.

EXAMPLE 3 By the use of 1.54 grams of N-Byy-dihYdlOXY- propyl N phenyl 2 methoxy 5 chloroaniline in place of N-fl-hydroxyethyl-N-phenylm-toluidine in Example 1, 1.3 grams of dye were obtained as a fine, dark powder. It colors cellulose acetate textile materials blue shades of good depth and brightness. The dyeings possess good light fastness and very good fastness to gas and have excellent discharge properties.

EXAMPLE 4 098 gram (0.005 mole) of 2-amino-5-nitro- 4-trifiuoromethylthiazole were diazotized and the diazonium compound obtained was coupled with 1.14 gram (0.005 mole) of N-5,'y-dihydroxypropyl i l 2 pyridyl) m toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with procedure described in Example 1. 1.58

were obtained. This compound colors cellulose acetate textile materials bright greenish-blue shades which have good fastness to light and excellent fastness to gas. Discharge prints were sharp and pure White. The compound also colors nylon, wool and silk greenish-blue shades.

EXAIVIPLE 5 were aode to a solution of propyhN-phenyl i chloroaniline in 10 cc. of a 1:5 mixture of pr picnic acid-acetic acid. Upon working up the reaction mixture in accordance with the procedure described in Example 1, about 1.5 grams of dye were obtained as a dark powder. It colors cellulose acetate textile materials violet shades having iastness to light and excellent fastness to gas.

EXAMPLE 6 By the use of 1.77 grams of N-B, -dihydroxypropyl-N-p-xenyl-in-chloroaniline in place of N-B-hydroxyethyhN-phenyl-m-toluidine in ample 1, 1.?2 grams of dye were obtained as a dark powder. It colors cellulose acetate textile materials bright violet shades having good fastness to light and excellent fastness to gas.

EXAIVH LE 7 1.33 of 2-amino-5-nitro l- (m-nitrophenyl -thiazole were diazctized and the diazonium compound obtained was coupled with 1.44 grams of N-fl,wdihydroxypropyhN-phenyl-2-methoxy- 5-!nethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the procedu e described in Example 1. 1.47 grams of dye were obtained as a dark powder. It colors cellulose acetate textile materials blue-green shades having good fastness to light and excellent fastness to gas. The dye compound also colors nylon, wool and silk textile materials blue-green shades.

EXAMPLE 8 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.13 grams of N-fl-hydroxyethyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials bluish-violet shades.

EXAMPLE 9 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2. 13 grams of N-B y-dlhydl'OXypropyl N phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials bluish-violet shades.

EXAMPLE 10 1.59 grams of 2-amino-4-methyl-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.13 grams of N c hydroxyethyl N phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

EXAMPLE 11 1.73 grams of 2-amino- 1-ethyl-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.27 grams of N-,8- hydroxyethyl N phenyl m toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 12 2.29 grams of 2-amino-4-n-hexyl-5-nitrothiw zole were diazotized and the diazonium compound obtained was coupled with 3.08 grams of N 9, dihydroxypropyl N phenyl 2 methoxy 5 chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

7 EXAMPLE 14 1.70 grams of 2-amino-4-cyano-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.28 grams of N-B- hydroxyethyl N pyridyl m toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 15 2.13 grams of 2-amino-4-trifiuoromethyl-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.49 grams of N r3 hydroxyethyl N pyridyl m chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 16 EXAMPLE 1'7 2.66 grams of 2-amino-4- (o-nitrophenyl) nitrothiazole were diazotized and the diazonium compound obtained with coupled with 2.43 grams of N {3 hydroxyethyl N phenyl m methoxyaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

By the use of 2.85 grams of N-B-hydroxyethylr N-phenyl-m-n-butoxyaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials blue shades.

EMMPLE 18 2.66 grams of 2-amino-4-(m-nitrophenyD-S- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.27 grams of hydroxypropyl-l l-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

By the use of 2.27 grams of N-e-hydroxypropyl-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials blue shades.

EXANLPLE 19 2.66 grams of 2-a1nino-4-(p-nitrophenyl)-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.4-1 grams of N-t-hydroxybutyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound obtained colors cellulose acetate textile materials blue shades.

By the use of 2.55 grams of N-s-hydroxyamyl- N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 20 2.55 grams of 2-amino-4-(p-chlorophenyl)-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 3.20 grams of N-Bw-dihydroxypropyl-N-xenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 21 3.0 grams of 2-amino-4-(o-bromophenyD-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 3.55 grams of N-lm-dihydroxypropyl-NXenyl-m-chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 22 2.39 grams of Z-amino--(o-fluorophenyD-S- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.79 grams of N-fi -dihydroXypropyl-N-pyridyl-m-chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 23 2.35 grams of 2-amino-4-(p-methylphenyD-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.58 grams of N B hydroxyethyl N pyridyl 2 methoxy-5-methylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials greenish-blue shades.

EXAMPLE 24 2.77 grams of 2-amino-4-(p-n-butylphenyD-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.70 grams of N-fl-hydroxyethyl-N-phenyl-m-acetaminoaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials greenish-blue shades.

EXAMPLE 25 2.55 grams of 2-amino-4-(o-chlorophenyl)-5 nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.57 grams of N -fl,'y-dihydroxypropylN phenyl-m-toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye, compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 26 2.39 grams of 2-amino-4-(p-fiuorophenyD-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.78 grams of N on; dihydroxypropyl-N-phenyl-rn-chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

EXAMPLE 27 2.35 grams of 2-amino-4-(o-methylph nyD-5- nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.43 grams of N-fin/-dihydroxypropyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried. out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 28 1.45 grams of 2-amino-5-nithothiazole were diazotized and the diazonium compound obtained was coupled with 1.97 grams of N-ethyl-N' phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 1.83 grams of N-methyl-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials violet shades.

EXAMPLE 29 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.25 grams of N-isopropyl-N- phenyl-m-toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

By the use of 2.39 grams of N-n-butyl-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 30 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazcnium compound obtained was coupled with 3.44 grams of N-n-decyl-N- phenyl m-chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By the use of 2.89 grams of N-n-hexyl-N- pyridyl-m-chloroaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 3 l 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.27 grams of N dmethoxyethyl-N-phenylaniline. Diazotization, coupling recovery of the dye compound formed were carried out in accordance with the general proc'edure described in Example 1. The dye compound obtained colors cellulcse acetate textile materials violet shades.

By the use of 2.71 grams of N-c-ethoxyethyl- N-phenyl-m-ethoxyaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials violet shades.

EXAMPLE 32 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.55 grams of N-[i-n-propoxyethyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.84 grams of N-y-n-butoxyethyl- N-pyridyl-m-toluidine in the above example, a dye compound is obtained which colors cellulose acetate textile materials blue shades.

EXAMPLE 33 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.22 grams of N-c-cyanoethyl- N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.78 grams of N-E-cyanopentyl- N-phenyl-m-toluidine in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 35 1.45 grams of Z-amino-S-nitrothiazole were diazotized and the diazoniuin compound obtained was coupled with 2.37 grams of l 2-y-cyan0propy1- N-pyridylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye com pound obtained colors cellulose acetate textile materials reddish-violet shades.

By the use of 2.79 grams of N-6-cyanobutyl-N- pyridyl-m-ethylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAIWPLE 36 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.93 grams of N-c-suliatoethyl- N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textil materials reddish-blue shades.

11 By the use of 3.83 grams of N-fl-sulfato-npropyl-N-xenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 37 EXAMPLE 38 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 3.06 grams of N-B-phosphatoethyl-N-phenyl-m-toluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials blue shades.

By the use of 3.37 grams of N-e-phosphatoamyl-N-pyridylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 39 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.76 grams of N-p-phosphonoethyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By the use of 2.77 grams of N-B-phosphonoethyl-N-pyridylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 40 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 3.04 grams of N-a-phosphonobutyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By the use of 3.18 grams of N-e-DhOSPhOIlO- amyl-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 41 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 1.95 grams of N-vinyl-N-phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.09 grams of N-ally1-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 42 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 1.96 grams of N-vinyl- N-pyridylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.10 grams of N-allyl-N-pyridylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 43 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.71 grams of N-vinyl- N-xenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.35 grams of N-allyl-N-xenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 44 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.23 grams of N-methallyl N phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.23 grams of N-crotyl-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials violet shades.

EXAMPLE 45 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.41 grams of phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials violet shades.

By the use of 2.42 grams of pyridyl aniline in the above example, a dye compound 1s obtained which colors cellulose acetate textile materials violet shades.

EXAMPLE 46 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.69 grams of Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 13 l. The dye compound obtained color cellulose acetate textile materials reddish-blue shades.

By the use of 2.83 grams of N-CHZCOOCHQCH2CH2CH3-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials violet shades.

EXAMPLE 47 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.90 grams of cellulose acetate textile materials violet shades.

By the use of 2.97 grams of N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 48 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.69 grams of N CH2CHzCI-I2COOCH3 N-phenylaniline Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By the use of 2.83 grams of N-CHzCI-IzCI-lzCOOCzHs-N-phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile material reddish-blue shades.

EXAMPLE 49 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 3.11 grams of NCH2CH2CH2COOCH2CI-ECH2CH3 N-phenylaniline Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By use of 2.42 grams of ance with the general procedure described in Example 1. The dye compound obtained colors Cir cellulose acetate textile materials reddish-blue shades.

By the use of 3.45 grams of N -CH2CH2COOC2H5N -xenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 51 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.77 grams of N-B-sulfoethyl-N- phenylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials reddish-blue shades.

By the use of 3.53 grams of N-p-sulfoethyl-N- xenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

EXAMPLE 52 1.45 grams of 2-amino-5-nitrothiazole were diazotized and the diazonium compound obtained was coupled with 2.78 grams of N-p-sulfoethyl-N- pyridylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound ob tained colors cellulose acetate textile materials reddish-blue shades.

By the use of 3.06 grams of N-a-sulfobutyl-N- phenylaniline in the above example, a dye compound is obtained which colors cellulose acetate textile materials reddish-blue shades.

The compounds tabulated hereinafter further illustrate the compounds of our invention. These compounds are prepared by diazotizing the diazo components named hereinafter and coupling the diazonium compounds obtained with the coupling components named hereinafter. The color given is that which the compounds color cellulose acetate. The diazotization, coupling and recovery operations are carried out in accordance with the procedure described hereinbefore.

Table 1 [Diazo components: 2-amino-5-nitrothiazolc, Z-amino-i-methyl-S- nitrothiazolc and 2-amino-4-phenyl-5-nitrothiazole] Coupling Component Color 1. N-fi-hydroxycthyl-N-ph enyl-m-toluidinc reddish-blue. 2. N-B-hydroxyethylN'-phcnyl-mpthybmilin Do. 3. N-fl-hydroxyethylN'-phenyl-m-methoxyan no... Do. 4. N-B-hydroxyethyl-N-phony1-1n-ethoxyanili Do. N-B,ydihydroxypropyl-N-phenyl-mtoluid Do. 6. N-B :-dihyrlroxypropyl-N-phenyl-m-mctlioxy- Do.

aniline. 7. N-Byy-dihydroxypropyl-N-phcnylanilino Do. 8. N-fl,- -dihydroxypropyl-N-Xenyl-m-toluidine Do. 9. N- -hydroxypropyl-N-Z-pyridyl-In-toluidine Do. 10. N-- methoxy-fl-hydroxypropyl-N-phcuylanilinc violet. ll. N-fl, -6-trihydroxybut l-N-phenyLm-toluidine i'ed lisl1-blue. 12. N -,8, y-dihydroxypropy l-phenyl-m -acctaminoaniline bl us. 13.

Do. 15. reddish-blue. l6. Do. 17. idylamlme Do. 18. yl phcnylqh-toluidine Do. 19. N phenyl-m-toluidine Do. 20. henyl-m-toluidine Do. 21. N-B-phosphonoeth3 .--phcnyl-m-methoxyauilinc Do. 25!. N-y-phosphonopropyl-N-phenylm-rnethoxy aniline Do. 23. li-B-sulfaoethyl-N-4-pyri(lyl-ni-chloroaniline violet. 24. N f3 methyl-fin-dihydroxypropyl-N-p-chlorophenyl-m-toluidinc re ddish-blue Table 2 2-amino-4-cyano-5-nitrothiazole, 2-amino-4- [Diazo components:

and 2-amino-4-m-nitrophenyl-5- trifiuoromethyl-nitrothiazole nitrothiazole] Coupling Component Color 1. N-fi'hydroxyethyl-N-phenyl-m-toluidine blue. 2. N-fi-hydroxyethyl-N-phenyl-1n-ctl1ylaniline Do. 3. N-fi-hydroxyethyl-N-phenyl m-methoxyaniline Do. 4. N-fl-hydroxyothyl-N-phonyl-m-ethoxyaniline Do. 5. N-B, dihydroxypropyl-N-phenyl-m-toluidine. Do. 0. N-fl,'r-dihydroxypropyl-Nphenyl-m-methoxy aniline Do. 7. N-fl,'y-rlihydroxypropyl- -phenylani1ine Do. 8. N-fl, -dihydroxypropyl-N -xeuy1-m-toluidine Do. 0. N -hydroxypropyl-N-2-pyridy1-m-toluidine Do. 10. N -mothoxy-B-liydroxypropyl-N-phenylaniline reddish-blue. 11. N fi t-trihy roxybutyl-N-plmnyl-m-toluidine. blue. 12. vo xypropyl-N-phenyl-m-acetaminogreenish-blue.

aniline Do. 14. N-B,-y-dihydror propyl-N-phenyl-m-hutyrl- Do.

ammoaniline 15. N-fi-sulfoethyl-N-pl nyLm-toluidinc... blue. 10. N-B-sulfon-propyl l -pheny1-m-toluidin Do. 17. N-5-sullobutylN-2-pyridylanilinc Do. 18. N-fi-pbosphatoethyl-N-phenyl-m-toluidinc.. Do. 19. Nfi-sulfatoetliyl-N-phenyl-m-toluidine Do. 20. N-t-sulfatobutyl-Y-phenyl m-toluidine Do. 21. N-fi-phosphouocthyl-N -phenyl-in-metl1oxyaniline Do. 22. N- phosphonopropyl-N-phenyl-m-methoxyouilinc. Do. 23. N-B-sulfatoethyl-N- l-pyridyl-m-chloroaniline Do. 24. N-flmethyl- 3, -dihydroxypropyl-N-p-ch1orophenyl-m-toluidine Do.

The sulfatoalkyl, the sulfoalkyl, the phos-- phatoalkyl and the phosphonoalkyl groups which may be present in our new dye compounds can be present in their free acid form or any suitable salt form such as, for example, the Na, K, NH4, Mg, Ca or Li salt form.

In order that the preparation of the azo compounds of our invention may be entirely clear the preparation of certain intermediates used in their manufacture is described hereinafter.

2-amino-4phenylthiazole 160 grams of bromine were added dropwise, with stirring, to a slurry of 120 grams of acetophenone and 152 grams of thiourea in a suitable reaction vessel. Heat was evolved and stirring became diflicult.

The reaction mixture was heated on a steam bath overnight after which 2.5 liters of hot water (85 C. were added The reaction mixture was stirred to effect solution and then filtered While hot. On cooling, the hydrobromide salt of 2- amino-4-phenylthiazole crystallized. Then concentrated ammonium hydroxide was added to the cold reaction mixture until it became slightly alkaline. The reaction mixture was filtered and the 2-aznino-4-phenylthiazole collected on the filter was washed once with water and dried. A yield of 126 grams was thus obtained. Upon recrystallization from ethyl alcohol 2-amino-4- phenylthiazole melting at 144 C.-l46 C. was obtained.

2-amz'no-4-(m-nitrophenyl) thiazole 160 grams of bromine were added dropwise, with stirring, to a mixture of 165 grams of mnitroacetophenone and 152 grams of thiourea in a suitable reaction vessel. To ward the end of the bromine addition the reaction mixture became a slurry.

After heating on a steam bath overnight, the reaction product was dissolved by pouring the reaction mixture into 4 liters of hot water and the resulting solution was filtered while hot. Upon cooling, the hydrobromide salt of 2-amino-4- (mnitrophenyl) thiazole crystallized. Then concentrated ammonium hydroxide was aded to the cold reaction mixture until it became slightly alkaline. The reaction mixture was filtered and the 2 amino 4 (m nitrophenyl) thiazole collected on the filter was washed once with water and dried. The yield of crude product was 87% of the theory. Upon recrystallization twice from ethyl alcohol 2 amino 4 (m nitrophenyl) thiazole melting at 178 0-180 C. was obtained.

2-amino-4" (m-nitrophenyl) -5nit1'othiazoZe 60 grams of 2-amino-4-(m-nitrophenyl)thiazole were dissolved at 15 C. in 300 cc. of H2804. 13.3 cc. of fuming nitric acid (90 density 1.5, 5% excess) were added at 10 C.-15 C. and the reaction mixture was allowed to stand overnight. Then the reaction mixture was stirred into ice and the reaction product filtered off. The reaction product was slurried with sodium bicarbonate until neutral and then with water. Upon recrystallization from nitrobenzene the 2- amino-4- (m-nitrophenyl) -5-nitrothiazole reaction product melted at 236-237" C.

2-acetamido-4-phenylthiaeole 15 grams of 2-arnino-4-phenylthiazole were heated on a steam bath with 50 cc. of acetic anhydride. Solution first occurred and then the reaction product precipitated. The reaction mixture was cooled, poured into water and stirred until excess acetic anhydride had reacted. Then the reaction mixture was filtered and the 2- acetamido-4-phenylthiazole collected on the filter was dried. Upon recrystallization from ethyl alcohol it melted at 206 C.-208 C.

2-amino-4-phenyl 5-nitrothia2oZe The 2-acetamido-4phenylthiazole prepared as described above was nitrated in sulfuric acid with fuming nitric acid in accordance with the procedure described in connection with z amino- 4 (m nitrophenyl) 5 nitrothiazole. Upon recrystallization from an acetic acid-water mixture the 2-acetamido-4-phenyl-5-nitrothiazole reaction product melted at 215 C.-224 C. 7 grams of the acetamido reaction product were hydrolyzed to the amino compound using 45 cc. of HCl, 90 cc. of H20 and 90 cc. of acetic acid. The 2-amino4-phenyl-5-nitrothiazole thus obtained was recrystallized from nitrobenzene. The purified product sintered and darkened at 245 C. and decomposed at 260 C.

2 -amino- 4-triflu0romethylthiazole This compound was prepared by reacting 14 grams (0.0955 mole) of B-chloro-LLl-trifiuoro- 2-propanone and 7.26 grams of thiourea in 50 cc. of water for 4 hours on a steam bath. After making the reaction mixture slightly basic with sodium carbonate a yellow precipitate of 2- amino-4-trifluoromethylthiazo1e formed and was recovered by filtration and dried. It melted at 58 C.60 C.

This compound is prepared by nitrating 2- amino-4-trifluoromethylthiazole at 5 C.-10 C. in sulfuric acid with fuming nitric acid and allowing the reaction mixture to warm to room temperature overnight. The reaction mixture is then drowned on ice, neutralized with sodium carbonate and the precipitated 2-amino-4-trifiuoromethyl- 5 -nitrothiazole is filtered oil, washed with water and dried.

2-amz'no-4-cyanothiaeole This compound is prepared by reacting equal 1? molar quantities of thiourea and bromopyruvonitrile in ethyl alcohol.

Z-amz'no-4-cyano-5-nitrothiazole Z-amz'no--methylthiazole This compound melting at 44 C.-45 C. is obtained in a 70-75% yield by reacting thiourea and chloroacetone together in accordance with the procedure described by Byers and Dickey in Organic Syntheses, Collective volume 2, page 31 (1943).

2-amino-4-alkylthiazole the general formula:

compounds having HO O-NH9 wherein R represents an alkyl group having 1 to 6, inclusive, carbon atoms are preparedby'reacting thiourea with a ketonehaving the formula:

wherein 36:. represents an alkyl group having 1 to 6, inclusive, carbon atoms. The reaction is carried out in accordance with the procedure used in preparing 2-amino-4-methylthiazo1e.

Compounds having the formula:

OzN-C C-NH:

RCN

wherein R represents an alkyl group having 1 to 6, inclusive, carbon atoms are prepared by nitrating the corresponding unnitrated compound with fuming nitric acid in sulfuric acid at a temperature of about C. The reaction is carried out using the general procedure described in connection with the preparation of 2- amino-4-trifiuoromethyl-5-nitrothiazole.

2 amino 4. phenyl 5 nitrothiazole and Z-amino-- (m-nitrophenyl) -5nitrothiazole also can be prepared by the procedures referred to in chapter 8 of Organic Reactions, volume VI, published by John Wiley and Sons, Inc. (e. g. see pages 330 and 398). The procedures described or indicated herein are used in the preparation of the other Z-amino--substituted phenyl-5-nitrothiazo-le compounds referred to herein.

The azo dye compounds of our invention can be applied to the textile materials named hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignum sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 30 C.90 C. and maintained at this temperature until dyeing is complete, usually onehalf to two hours. From time to time through- 18 out the dyeing operation, the material is worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, to 3% (by weight) of that of the textile material although lesser or greater amounts of dye can be employed.

The term xenylfas used in the examples and in Tables 1 and 2 refers to p-xenyl. The term pyridyl as used in the examples and in Tables 1 and 2, except as otherwise indicated, refers to Z-pyridyl.

Related azo compounds are disclosed in our copendin application Serial No. 233,243, filed June 23, 1951. This application is now Patent No. 2,659,719 issued November 17, 1953.

We claim:

1. The azo compounds having the general formula:

wherein R represents a member selected from the group consisting of an alkylgrouphaving 1 to 10, inclusive, carbon atoms, an alkoxyalkyl group having 3 to 6, inclusive, carbon atoms, a hydroxyalkyl group having 2 to 5, inclusive, carbon atoms, a cyanoalkyl group having 2 to 6, inclusive, carbon atoms, a sulfoalkyl group having 2 to 4, inclusive, carbon atoms, a sulfatoalkyl group havin 2 to 5, inclusive, carbon atoms, a phosphatoalkyl group having 2 to 5, inclusive, carbon atoms, a phosphonoalkyl group having 2 to 5, inclusive, carbon atoms, a ,S-nitroethyl group, an alkenyl group having 2 to 4, inclusive, carbon atoms and a -(CH2)mCOOR2, wherein m is selected from 1, 2 and 3 and R2 represents an alkyl group having 1 to 4, inclusive, carbon atoms, R1 represents a member selected from the group consisting of a phenyl group and a xenyl group, X represents a member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6, inclusive, carbon atoms, a cyano group, a trifluoromethyl group and a group, wherein Q represents a member selected from the group consisting of a hydrogen atom, a nitro group, a chlorine atom, a bromine atom and an alkyl group having 1 to 4, inclusive, carbon atoms, Z represents a member selected from the group consisting of an alkyl group having 1 to a, inclusive, carbon atoms, an alkoxy group having 1 to 4, inclusive, carbon atoms, a chlorine atom, a bromine atom, a fluorine atom and a group, wherein Y represents an alkyl group having 1 to 3, inclusive, carbon atoms and n is selected from 0, l and 2.

2. The azo compounds having the general formula:

wherein R represents a hydroxyalkyl groups having 2 to 5, inclusive, carbon atoms and Z represents a halogen atom having an atomic weight of from 19 to 80.

4. The azo compounds having the general formula:

wherein R represents a hydroxyalkyl group having 2 to 5, inclusive, carbon atoms.

5. The azo compound having the formula:

OHzCHaOH HC-N 6. The azo compound having the formula:

CHzCHOHCHzOH '7. The azo compound having the formula:

OCH:

CHzCHOHCHzOH 8. The azo compound having the formula:

CHaCHOHCHaOH 9. The azo compound having the formula:

CHzCOHOHzOH References Cited in the file of this patent FOREIGN PATENTS Country Date Great Britain Feb. 22, 1943 Great Britain Apr. 15, 1947 

2. THE AZO COMPOUNDS HAVING THE GENERAL FORMULA: WHEREIN R REPRESENTS A HYDROXYALKYL GROUP HAVING 2 TO 5, INCLUSIVE, CARBON ATOMS AND Z REPRESENTS AN ALKYL GROUP HAVING 1 TO 4, INCLUSIVE, CARBON ATOMS. 